Supporting Information. Bioactive Constituents of Glycyrrhiza uralensis (Licorice): Discovery of the Effective Components of a Traditional Herbal
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1 Supporting Information Bioactive Constituents of Glycyrrhiza uralensis (Licorice): Discovery of the Effective Components of a Traditional Herbal Medicine Shuai Ji, Ziwei Li, Wei Song, Yongrui Wang, Wenfei Liang, Kai Li, Shunan Tang, Qi Wang, Xue Qiao, Demin Zhou, Siwang Yu, * and Min Ye * State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, 38 Xueyuan Road, Beijing 1191, People s Republic of China * Corresponding authors. Tel.: Fax: address: swang_yu@bjmu.edu.cn (S.W. Yu) or yemin@bjmu.edu.cn (M. Ye). 1
2 List of Contents Experimental 1. Isolation and structural characterization of licorice compounds. 2. Electronic circular dichroism (ECD) spectral calculations for compounds UHPLC/UV analysis for chemical profiling of licorice extract and mixed standards. 4. Protective effects of licorice EtAc extract on CCl 4 -induced mice liver damage. Table S1. Bioactivity screening results (fold of control for Nrf2 activation activity and inhibition rates for the other activities) of licorice extracts and compounds Scheme S1. Strategy to discover the effective components of licorice. Chart S1. Structures of compounds isolated from Glycyrrhiza uralensis. Fig. S1. Comparison of the calculated ECD spectra for (3R)-1, (3R)-3, (3R,4R)-2, and their enantiomers, with the experimental ECD spectra for 1, 3 and 2. Fig. S2. (A) Dose-dependent activation effects of 46 on luciferase activity of HepG2 cells stably transfected with Nrf2 luciferase reporter. (B) Cytotoxicity of 46 against HepG2 cells at different concentrations. Fig. S3. UHPLC/UV chromatograms of licorice water crude extract (A), licorice EtH crude extract (B), licorice EtAc extract (C) and licorice n-buh extract (D) at 254 nm. Fig. S4. The chemical-bioactivity correlation of licorice. Fig. S5. The most active compounds for (A) Nrf2 activation, N inhibition, NF-κB inhibition, H1N1 inhibition, cytotoxic (HepG2, SW48, A549 and MCF7 cells) and (B) PTP1B inhibition, tyrosinase inhibition, AChE inhibition activities. Fig. S6. The protective effects of licorice EtAc extract against CCl 4 -induced mice liver damage. (A) Effects of licorice EtAc extract on mice hepatic GSH level after CCl 4 treatment. (B) Effect of licorice EtAc extract on mice serum ALT, AST and LDH levels after CCl 4 treatment. (C) Effect of licorice EtAc extract on the histological changes of mice liver after CCl 4 treatment. *p <.5; **p <.1; H&E 2
3 stained slices were observed under 4 magnification. Fig. S7. Flow chart for the isolation of compounds 74 76, and Fig. S8. Flow chart for the isolation of compounds Fig. S9 1 H NMR spectrum of glycyuralin A (1) in DMS-d 6 (4 MHz). Fig. S1 13 C NMR spectrum of glycyuralin A (1) in DMS-d 6 (1 MHz). Fig. S11 HMBC spectrum of glycyuralin A (1) in DMS-d 6 (4 MHz). Fig. S12 HSQC spectrum of glycyuralin A (1) in DMS-d 6 (4 MHz). Fig. S13 1 H- 1 H CSY spectrum of glycyuralin A (1) in DMS-d 6 (4 MHz). Fig. S14 IR spectrum of glycyuralin A (1). Fig. S15 HRESIMS spectrum of glycyuralin A (1). Fig. S16 1 H NMR spectrum of glycyuralin C (3) in DMS-d 6 (4 MHz). Fig. S17 13 C NMR spectrum of glycyuralin C (3) in DMS-d 6 (1 MHz). Fig. S18 HMBC spectrum of glycyuralin C (3) in DMS-d 6 (4 MHz). Fig. S19 HSQC spectrum of glycyuralin C (3) in DMS-d 6 (4 MHz). Fig. S2 1 H- 1 H CSY spectrum of glycyuralin C (3) in DMS-d 6 (4 MHz). Fig. S21 DEPT 135 spectrum of glycyuralin C (3) in DMS-d 6 (1 MHz). Fig. S22 DEPT 9 spectrum of glycyuralin C (3) in DMS-d 6 (1 MHz). Fig. S23 IR spectrum of glycyuralin C (3). Fig. S24 HRESIMS spectrum of glycyuralin C (3). Fig. S25 1 H NMR spectrum of glycyuralin B (2) in acetone-d 6 (4 MHz). Fig. S26 13 C NMR spectrum of glycyuralin B (2) in acetone-d 6 (1 MHz). Fig. S27 HMBC spectrum of glycyuralin B (2) in acetone-d 6 (4 MHz). Fig. S28 HSQC spectrum of glycyuralin B (2) in acetone-d 6 (4 MHz). Fig. S29 1 H- 1 H CSY spectrum of glycyuralin B (2) in acetone-d 6 (4 MHz). Fig. S3 DEPT 135 spectrum of glycyuralin B (2) in acetone-d 6 (1 MHz). Fig. S31 IR spectrum of glycyuralin B (2). Fig. S32 HRESIMS spectrum of glycyuralin B (2). Fig. S33 1 H NMR spectrum of glycyuralin D (4) in DMS-d 6 (4 MHz). Fig. S34 13 C NMR spectrum of glycyuralin D (4) in DMS-d 6 (1 MHz). Fig. S35 HMBC spectrum of glycyuralin D (4) in DMS-d 6 (4 MHz). 3
4 Fig. S36 HSQC spectrum of glycyuralin D (4) in DMS-d 6 (4 MHz). Fig. S37 1 H- 1 H CSY spectrum of glycyuralin D (4) in DMS-d 6 (4 MHz). Fig. S38 DEPT 135 spectrum of glycyuralin D (4) in DMS-d 6 (1 MHz). Fig. S39 DEPT 9 spectrum of glycyuralin D (4) in DMS-d 6 (1 MHz). Fig. S4 IR spectrum of glycyuralin D (4). Fig. S41 HRESIMS spectrum of glycyuralin D (4). Fig. S42 1 H NMR spectrum of glycyuralin E (5) in DMS-d 6 (4 MHz). Fig. S43 13 C NMR spectrum of glycyuralin E (5) in DMS-d 6 (1 MHz). Fig. S44 HMBC spectrum of glycyuralin E (5) in DMS-d 6 (4 MHz). Fig. S45 HSQC spectrum of glycyuralin E (5) in DMS-d 6 (4 MHz). Fig. S46 1 H- 1 H CSY spectrum of glycyuralin E (5) in DMS-d 6 (4 MHz). Fig. S47 DEPT 135 spectrum of glycyuralin E (5) in DMS-d 6 (1 MHz). Fig. S48 DEPT 9 spectrum of glycyuralin E (5) in DMS-d 6 (1 MHz). Fig. S49 IR spectrum of glycyuralin E (5). Fig. S5 HRESIMS spectrum of glycyuralin E (5). Fig. S51 1 H NMR spectrum of glycyuralin F (6) in DMS-d 6 (4 MHz). Fig. S52 13 C NMR spectrum of glycyuralin F (6) in DMS-d 6 (1 MHz). Fig. S53 HMBC spectrum of glycyuralin F (6) in DMS-d 6 (4 MHz). Fig. S54 HSQC spectrum of glycyuralin F (6) in DMS-d 6 (4 MHz). Fig. S55 1 H- 1 H CSY spectrum of glycyuralin F (6) in DMS-d 6 (4 MHz). Fig. S56 DEPT 135 spectrum of glycyuralin F (6) in DMS-d 6 (1 MHz). Fig. S57 DEPT 9 spectrum of glycyuralin F (6) in DMS-d 6 (1 MHz). Fig. S58 IR spectrum of glycyuralin F (6). Fig. S59 HRESIMS spectrum of glycyuralin F (6). 4
5 1. Isolation and structural characterization of licorice compounds. The dried licorice crude drug (35 kg) was powdered and extracted with 95% (9 L 2 h 2) and 7% EtH (9 L 2 h 1) under reflux. After concentration in vacuo, the extract (1 L) was dispersed in H 2 and successively extracted with EtAc and n-buh. The n-buh extract (154 g) was separated on an AB-8 macroporous resin column eluted with EtH/H 2 (1 to 95%, v/v) to obtain fractions A E. Triterpenoid saponins (94 122) were obtained mainly from fractions B and D, which was reported in our previous publication [1]. Phenolic glycosides (74 93) were obtained from fraction A (2 g), which was firstly subjected to MCI gel column chromatography and eluted with 1%, 3%, 55% and 95% EtH to afford fractions AA AD. Fraction AA was chromatographed over DS C 18 with EtH/H 2 (1 to 95%, v/v) as the eluent to obtain fractions AAA AAC, all of which were further purified over Sephadex LH-2 and semi-preparative HPLC to yield liquiritin (82, 5 mg) [3], sophoraflavone B (9, 4 mg) [4] and syringic acid 4--glucopyranoside (93, 2 mg) [5]. Fraction AB was fractionated on an MCI gel column eluted with EtH/H 2 (1 to 95%, v/v) to obtain fractions ABA ABE, and they were further purified over Sephadex LH-2 and semi-preparative HPLC to obtain liquiritigenin 7,4'--diglucopyranoside (74, 165 mg) [4], glucoliguiritin apioside (75, 34 mg) [6], vicenin-2 (76, 165 mg) [7], apigenin 6-C-rhamnopyranosyl-8-C-[6'''-(3-hydroxy-3-methylglutaroyl)-glucopyranoside] (83, 12 mg) [8], isoliquiritigenin 4,4'--diglucopyranoside (79, 12 mg) [9] and isoviolanthin (8, 33 mg) [1]. Fraction AC was also subjected to MCI gel column chromatography eluted with EtH/H 2 (1 to 95%, v/v) as the eluent to produce ACA ACC. They were further purified over DS C 18 and semi-preparative HPLC to yield liquiritin apioside (81, 4 mg) [11], 7,4'-dihydroxyflavone 7--glucopyranoside (91, 6 mg) [12] and daidzin (92, 5 mg) [13]. Using the similar method with fraction AC, isoliquiritin apioside (84, 3 mg) [14], ononin (85, 5 mg) [15], isoliquiritin (86, 49 mg) [3] and glycyroside (89, 18 mg) [4] were obtained from fraction AD by MCI, Sephadex LH-2 and semi-preparative HPLC. In addition, schaftoside (77), isoschaftoside (78), neoliquiritin (87) and neoisoliquiritin (88) were purchased from Mansite Bio-Technology Co., Ltd. (Chengdu, China). Free phenolics (1-73) were mainly isolated from the EtAc extract, and the isolation and structural characterization of 29, 32, 48 and 5 have been reported in our recent publication [2]. In general, the EtAc extract (128 g) was chromatographed over silica gel using petroleum ether/etac (1: to 1:1, v/v) as the eluent to produce fractions A J. Fraction B (6 g) was separated on a silica gel column eluted with 5
6 petroleum ether/acetone (1: to 1:1, v/v) to obtain fraction BA BE. Fraction BD was further subjected to polyamide column chromatography eluted with EtH/H 2 (1 to 9%, v/v) to yield fraction BDA BDI. Fractions BDC, BDF and BDH were purified over Sephadex LH-2 and semi-preparative HPLC to obtain licoisoflavanone (58, 18 mg) [16], abiochanin A (59, 2 mg) [17], glyasperin S (6, 2.5 mg), glyasperin C (62, 5 mg) [18], 3-methoxy-9-hydroxy-pterocarpan (64, 32 mg) [19], 1-methoxy-phaseollin (65, 95 mg) [6], glabridin (66, 2 mg) [2], isolupalbigenin (67, 2 mg) [21], 6,8- diprenylgenistein (68, 2 mg) [22], 2'-hydroxy-isolupalbigenin (69, 2 mg) [23], isoderrone (7, 6 mg) [24], licoricidin (71, 9 mg) [25] and licoisoflavone B (73, 1 mg) [16]. Fraction E (3 g) was subjected to MCI gel column chromatography and eluted with 3%, 4%, 5%, 6%, 7%, 8% and 9% EtH to afford fractions EA EG. Fraction EC was fractionated on a polyamide column eluted with CH 2 Cl 2 /MeH (1: to 1:1, v/v) to produce ECA ECN. Fractions ECC, ECD, ECI and ECK were further separated by DS C 18 columns and purified over semi-preparative HPLC to yield glycyrol (9, 82 mg) [26], semilicoisoflavone B (16, 12 mg) [27], kumatakenin (17, 5 mg) [28], licoricone (18, 18 mg) [29], glyasperin (1, 54 mg), glyasperin Q (2, 3 mg), glyasperin P (3, 2 mg), licoflavonol (2, 6 mg) [28], topazolin (21, 195 mg) [3], licoisoflavone A (22, 36 mg) [31], wighteone (23, 12 mg) [32], allolicoisoflavone B (24, 71 mg) [33], 5,7,4'-trihydroxy-3'-(3-methylbut-2-enyl)-3-methoxy flavone (25, 2 mg) [34], lupiwighteone (26, 2 mg) [35], glyasperin T (4, 5 mg), isolicoflavonol (28, 2 mg) [36], glycyfuranocoumarone A (29, 2 mg) [2], formononetin (3, 17 mg) [29], genkwanin (31, 3 mg) [37], glycyfuranocoumarin A (32, 7 mg) [2], isoglabrone (34, 2 mg) [38] and glyurallin A (35, 2 mg) [39]. Fraction EE was separated by silica gel column chromatography with CHCl 3 /MeH (1: to 1:1, v/v) as the eluent to obtain EEA EEE. Fractions EEA, EEC and EEE were further purified over Sephadex LH-2 and semi-preparative HPLC to obtain isoangustone A (1, 488 mg) [27], isoglycyrol (11, 84 mg) [26], 7--methylluteone (12, 41 mg) [4], glyasperin D (13, 14 mg) [18], dehydroglyasperin D (14, 5 mg) [41] and gancaonin I (15, 95 mg) [26]. Fraction EG was subjected to polyamide column chromatography eluted with CH 2 Cl 2 /MeH (1: to 1:1, v/v), and purified over Sephadex LH-2 and semi-preparative HPLC to yield angustone A (19, 7 mg) [42]. Fraction H (1 g) was subjected to MCI gel column chromatography and eluted with 1%, 3%, 5%, and 95% EtH to afford fractions HA HD. Fraction HB was chromatographed over silica gel and eluted with CHCl 3 /MeH (1: to 1:1, v/v) to produce fractions HBA HBH. Fractions HBD, HBF and HBH were further separated 6
7 by Sephadex LH-2 and purified over semi-preparative HPLC to yield liquiritigenin (6, 33 mg) [43], licoflavone A (61, 2 mg) [44], daidzein (63, 3 mg) [45] and glycyrin (8, 27 mg) [46]. Fraction HC was subjected to polyamide column chromatography with CH 2 Cl 2 /MeH (1: to 1:1, v/v) as the eluent to obtain fractions HCA HCD. Fractions HCA, HCB and HCC were further purified by DS C 18 columns and semi-preparative HPLC to yield 7-methoxy-2',4'-dihydroxy isoflavone (36, 3 mg) [47], 11b-hydroxy-11b,1-dihydromedicarpin (37, 6 mg) [48], kaempferol 3--methyl ether (38, 1 mg) [49], 2-one-4-methoxy-pyran (39, 2 mg) [5], isoliquiritigenin (42, 226 mg) [51], genistein (44, 6 mg) [52], kumatakenin B (45, 9 mg) [53], echinatin (7, 6 mg) [54], glycyfuranocoumarin B (48, 5 mg) [2], glyasperin R (5, 25 mg), glicoricone (51, 14 mg) [55] and pratensein (52, mg) [56]. Fraction HD was also subjected to polyamide column chromatography eluted with CH 2 Cl 2 /MeH (1: to 1:1, v/v) to obtain HDA HDI. Fractions HDC, HDE, HDG and HDH were further separated by DS C 18 columns and purified over semi-preparative HPLC to yield hirtellanine I (4, 6 mg) [57], glycyrrhiza-isoflavone C (41, 4 mg) [58], isoglycycoumarin (43, 16 mg) [49], luteone (46, 52 mg) [59], licocoumarone (47, 77 mg) [49], uralenol (49, 16 mg) [6], glycyfuranocoumarin C (5, 1 mg) [2], dehydroglyasperin C (53, 6 mg) [61], homobutein (54, 2 mg) [62], 6-C-prenylorobol (55, 22 mg) [63], kaempferol (56, 6 mg) [51], gancaonin L (57, 22 mg) [64] and glicophenone (72, 2 mg) [65]. Fraction I (5 g) was isolated by a silica gel column eluted with CHCl 3 /MeH (1: to 1:1, v/v) to obtain fractions IA IC. Fraction IB was subjected to MCI gel column chromatography eluted with EtH/H 2 (1 to 9%, v/v) to produce fraction IBB, which was further purified over Sephadex LH-2 and semi-preparative HPLC to obtain licoarylcoumarin (27, 63 mg) [49] and glycycoumarin (33, 5 mg) [36]. Echinatin (7): 1 H NMR (4 MHz, DMS-d 6 ) δ: 7.91 (1H, d, J = 15.6 Hz, H-β), 7.64 (1H, d, J = 15.6 Hz, H-α), 7.99 (2H, d, J = 8.4 Hz, H-2, 6 ), 6.87 (2H, d, J = 8.4 Hz, H-3, 5 ), 6.47 (1H, d, J = 2. Hz, H-3), 6.44 (1H, dd, J = 2., 8.4 Hz, H-5), 7.76 (1H, d, J = 8.4 Hz, H-6), 3.84 (3H, s, 2-CH 3 ), 1.21 (H, br s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-β), (C-α), (C=), 13.8 (C-2 ), (C-3 ), (C-4 ), (C-3 ), 13.8 (C-2 ), (C-1 ), (C-1), 16. (C-2), 99.1 (C-3), (C-4), 18.2 (C-5), 13.1(C-6), 55.5 (2-CH 3 ). Glycyrin (8): 1 H NMR (4 MHz, DMS-d 6 ) δ: 7.83 (1H, s, H-4), 6.87 (1H, s, H-8), 6.35 (1H, d, J = 2. Hz, H-3 ), 6.26 (1H, dd, J = 2., 8. Hz, H-5 ), 7.12 (1H, d, J = 8. Hz, H-6 ), 3.27 (2H, d, J = 8. Hz, H-1"), 5.1 (1H, t, J = 8. Hz, H-2"), 1.72 (3H, s, H-4"), 1.62 (3H, s, H-5"), 3.76 (3H, s, 5-CH 3 ), 3.87 (3H, s, 7-CH 3 ), 9.45 (1H, s, 7
8 H), 9.47 (1H, s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: 16.9 (C-2), (C-3), (C-4), 155. (C-5), (C-6), (C-7), 95.6 (C-8), (C-9), 17.5 (C-1), (C-1 ), (C-2 ), 13.1 (C-3 ), 16.3 (C-4 ), 16.7 (C-5 ), 132. (C-6 ), 22.7 (C-1"), (C-2"), (C-3"), 18.1 (C-4"), 25.8 (C-5"), 63.4 (5-CH 3 ), 56.8 (7-CH 3 ). Glycyrol (9): 1 H NMR (4 MHz, DMS-d 6 ) δ: 6.77 (1H, s, H-8), 7.16 (1H, d, J = 2. Hz, H-3 ), 6.95 (1H, dd, J = 2., 8.4 Hz, H-5 ), 7.71 (1H, d, J = 8.4 Hz, H-6 ), 3.32 (2H, d, J = 7.2 Hz, H-1"), 5.19 (1H, t, J = 7.2 Hz, ), 1.76 (3H, s, H-4"), 1.65 (3H, s, H-5"), 3.9 (3H, s, 5-CH 3 ). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), 12.2 (C-3), (C-4), (C-5), (C-6), (C-7), 99.2 (C-8), (C-9), 99.7 (C-1), (C-1 ), (C-2 ), 98.5 (C-3 ), (C-4 ), 114. (C-5 ), 12.4 (C-6 ), 22. (C-1"), (C-2"), 13.9 (C-3"), 17.7 (C-4"), 25.4 (C-5"), 62.4 (5-CH 3 ). Isoangustone A (1): 1 H NMR (4 MHz, DMS-d 6 ) δ: 8.23 (1H, s, H-2), 6.43 (1H, s, H-8), 6.66 (1H, d, J = 1.6 Hz, H-2 ), 6.88 (1H, d, J = 1.6 Hz, H-6 ), 3.23 (2H, d, J = 6.8 Hz, H-1"), 5.17 (1H, t, J = 7.2 Hz, H-2"), 1.67 (3H, s, H-4"), 1.62 (3H, s, H-5"), 3.23 (2H, d, J = 6.8 Hz, H-1'''), 5.17 (1H, t, J = 7.2 Hz, H-2'''), 1.67 (3H, s, H-4'''), 1.72 (3H, s, H-5'''). 13 H NMR (1 MHz, DMS-d 6 ) δ: (C-2), (C-3), 18.3 (C-4), (C-5), 111. (C-6), 162. (C-7), 92.9 (C-8), (C-9), 14.2 (C-1), (C-1 ), 12.4 (C-2 ), (C-3 ), (C-4 ), (C-5 ), 114. (C-6 ), 21. (C-1"), (C-2"), 13.7 (C-3"), 17.7 (C-4"), 25.5 (C-5"), 28.3 (C-1'''), 123. (C-2'''), 13.9 (C-3'''), 17.7 (C-4'''), 25.5 (C-5'''). Isoglycyrol (11): 1 H NMR (4 MHz, DMS-d 6 )δ: 6.63 (1H, s, H-8), 7.16 (1H, d, J = 1.6 Hz, H-2 ), 6.96 (1H, d, J = 1.6, 8.4 Hz, H-4 ), 7.71 (1H, d, J = 8.4 Hz, H-5 ),2.81 (2H, t, J = 6.4 Hz, H-1"), 1.83 (2H, t, J = 6.4 Hz, H-2"),1.34 (3H, s, H-4"), 1.34 (3H, s, H-5"), 3.95 (3H, s, 5-CH 3 ). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), 12.8 (C-3), (C-4), (C-5), (C-6), (C-7), 1.4 (C-8), (C-9), 1.4 (C-1), (C-1 ), 98.5 (C-2 ), (C-3 ), (C-4 ), 12.5 (C-5 ), (C-6 ), 16.2 (C-1"), 31. (C-2"), 75.9 (C-3"), 26.4 (C-4"), 26.4 (C-5"), 61.5 (5-CH 3 ). 7--methylluteone (12): 1 H NMR (4 MHz, DMS-d 6 ) δ: 8.24 (1H, s, H-2), 6.71 (1H, s, H-8), 6.36 (1H, d, J = 1.2 Hz, H-3 ), 6.27 (1H, dd, J = 1.2, 8.4 Hz, H-5 ), 6.98 (1H, d, J = 8.4 Hz, H-6 ), 3.25 (2H, d, J = 6.8 Hz, H-1"), 5.13 (1H, t, J = 6.8 Hz, H-2"), 1.72 (3H, s, H-4"), 1.62 (3H, s, H-5"), 3.91 (3H, s, 7-CH 3 ). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), (C-3), 18.6 (C-4), (C-5), (C-6), (C-7), 9.1 (C-8), (C-9), 12.6 (C-1), 18.6 (C-1 ), (C-2 ),
9 (C-3 ), (C-4 ), 16.2 (C-5 ), 131 (C-6 ), 21 (C-1"), 12.7 (C-2"), (C-3"), 17.6 (C-4"), 25.5 (C-5"), 56.4 (7-CH 3 ). Glyasperin D (13): 1 H NMR (4 MHz, DMS-d 6 ) δ: 3.92 (1H, t, J = 1 Hz, H-2), 4.15 (1H, m,h-2), 3.23 (1H, m,h-3), 2.73 (1H, dd, J = 1.4, 16.4 Hz, H-4), 2.77 (1H, ddd, J = 5.6, 6.5, 16.4 Hz, H-4), 6.23 (1H, s, H-8), 6.34 (1H, d, J = 2.4 Hz, H-3'), 6.2 (1H, dd, J = 2.4, 8.4 Hz, H-5'), 6.87 (1H, d, J = 8.4 Hz, H-6'), 3.14 (2H, m, H-1"), 5.9 (1H, t, J = 6.8 Hz, H-2"), 1.69 (3H, s, H-4"), 1.61 (3H, s, H-5"), 3.7 (3H, s, 5-CH3), 3.62 (3H, s, 7-CH3), 9.38 (1H, s, 2'-H), 9.11 (1H, s, 4'-H). 13 C NMR (1 MHz, DMS-d 6 ) δ: 69.3 (C-2), 3.7 (C-3), 25.5 (C-4), (C-5), (C-6), (C-7), 95.5 (C-8), (C-9), 18.1 (C-1), (C-1 ), (C-2 ), 12.6 (C-3 ), (C-4 ), 16.3 (C-5 ), (C-6 ), 22.2 (C-1"), (C-2"), (C-3"), 17.6 (C-4"), 25.4 (C-5"), 6.1 (5-CH3), 55.5 (7-CH3). Dehydroglyasperin D (14): 1 H NMR (4 MHz, DMS-d 6 ) δ: 4.89 (2H, s, H-2), 6.67 (1H, s, H-4),6.32 (1H, s, H-8), 6.34 (1H, d, J = 1.6 Hz, H-3 ), 6.25 (1H, d, J = 1.6, 8.4 Hz, H-5 ), 7.6 (1H, d, J = 8.4 Hz, H-6 ),3.16 (2H, d, J = 6.4 Hz, H-1"), 5.8 (1H, t, J = 6.4 Hz, H-2"),1.71 (3H, s, H-4"), 1.62 (3H, s, H-5"), 3.66 (3H, s, 5-CH 3 ), 3.74 (3H, s, 7-CH 3 ). 13 C NMR (1 MHz, DMS-d 6 ) δ: 67.3 (C-2), (C-3), (C-4), (C-5), (C-6), (C-7), 95.3 (C-8), (C-9), 19.9 (C-1), (C-1 ), (C-2 ), 12.8 (C-3 ), (C-4 ), 16.9 (C-5 ), (C-6 ), 22.1 (C-1"), (C-2"), (C-3"), 17.6 (C-4"), 25.5 (C-5"), 61.7 (5-CH 3 ), 55.7 (7-CH 3 ). Gancaonin I (15): 1 H NMR (4 MHz, DMS-d 6 ) δ: 7.18 (1H, s, H-3), 6.95 (1H, s, H-7), 6.46 (1H, d, J = 2. Hz, H-3 ), 6.36 (1H, dd, J = 2., 8.4 Hz, H-5 ), 7.57 (1H, d, J = 8.4 Hz, H-6 ), 3.29 (1H, d, J = 7.2 Hz, H-1"), 5.11 (1H, t, J = 7.2 Hz, H-2"), 1.73 (3H, s, H-4"), 1.62 (3H, s, H-5"), 3.96 (3H, s, 4-CH 3 ), 3.81 (3H, s, 6-CH 3 ), 1.18 (1H, s, 2 -H),9.61 (1H, s, 4 -H). 13 C NMR (1 MHz, DMS-d 6 ) δ: 15.9 (C-2), 1.3 (C-3), (C-4), 115. (C-5), 15.1 (C-6), 89.6 (C-7), (C-8), (C-9), 18.8 (C-1 ), (C-2 ), 12.9 (C-3 ), (C-4 ), 17.1 (C-5 ), (C-6 ), 22.3 (C-1"), (C-2"), (C-3"), 17.6 (C-4"), 25.3 (C-5"), 59.9 (4-CH 3 ), 56. (6-CH 3 ). Semilicoisoflavone B (16): 1 H NMR (4 MHz, DMS-d 6 ) δ: 8.34 (1H, s, H-2), 6.22 (1H, d, J = 1.6 Hz, H-6), 6.38 (1H, d, J = 1.6 Hz, H-8), 6.73 (1H, d, J = 1.6 Hz, H-2 ), 6.91 (1H, d, J = 1.6 Hz, H-6 ),6.37 (1H, d, J = 9.6 Hz, H-1"), 5.76 (1H, d, J = 9.6 Hz, H-2"), 1.39 (3H, s, H-4"), 1.39 (3H,s, H-5"), (1H, s, 5-H),1.89 (1H, s, 7-H), 8.98 (1H, s, 3 -H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), (C-3), 9
10 18.1 (C-4), 162. (C-5), 97.7 (C-6), (C-7), 93.7 (C-8), (C-9), 14.4 (C-1), (C-1 ), 122. (C-2 ), (C-3 ), 14.1 (C-4 ), (C-5 ), (C-6 ), 117. (C-1"), (C-2"), 76. (C-3"), 27.5 (C-4"), 27.5 (C-5"). Kumatakenin (17): 1 H NMR (4 MHz, DMS-d 6 ) δ: 6.37 (1H, d, J = 2.4 Hz, H-6), 6.74 (1H, d, J = 2.4 Hz, H-8), 7.98 (2H, d, J = 8.8 Hz, H-2, 6 ), 6.95 (2H, d, J = 8.8 Hz, H-3, 5 ), 3.8 (3H, s, CH 3 ), 3.86 (3H, s, CH 3 ), (1H, s, H), 1.28 (1H, s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), (C-3), 178. (C-4), 16.9 (C-5), 97.7 (C-6), (C-7), 92.3 (C-8), 16.3 (C-9), 15.2 (C-1), 12.4 (C-1 ), 13.6 (C-2 ), (C-3 ), (C-4 ), (C-5 ), 13.6 (C-6 ), 56. (CH 3 ), 59.7 (CH 3 ). Licoricone (18): 1 H NMR (4 MHz, DMS-d 6 ) δ: 7.99 (1H, s, H-2), 7.87 (1H, d, J = 8.4 Hz, H-5), 6.88 (1H, br d, J = 8.4 Hz, H-6), 6.8 (1H, br s, H-8), 6.32 (1H, s, H-5 ), 3.15 (2H, d, J = 6.8 Hz, H-1"), 5.11 (1H, t, J = 6.8 Hz, H-2"), 1.68 (3H, s, H-4"), 1.62 (3H, s, H-5"), 3.36 (3H, s, CH 3 ), 3.73 (3H, s, CH 3 ). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), (C-3), (C-4), (C-5), (C-6), (C-7), 12.1 (C-8), (C-9), 117. (C-1), 15.9 (C-1 ), (C-2 ), (C-3 ), (C-4 ), 95.3 (C-5 ), (C-6 ), 22.3 (C-1"), 124. (C-2"), (C-3"), 17.6 (C-4"), 25.5 (C-5"), 55.5 (CH 3 ), 6.6 (CH 3 ). Angustone A (19): 1 H NMR (4 MHz, DMS-d 6 ) δ: 8.11 (1H, s, H-2), 6.44 (1H, s, H-8), 6.36 (1H, d, J = 8. Hz, H-5 ), 6.73 (1H, d, J = 8. Hz, H-6 ), 3.23 (2H, d, J = 7.6 Hz, H-1"), 5.18 (1H, t, J = 7.6 Hz, H-2"), 1.71 (3H, s, H-4"), 1.62 (3H, s, H-5"), 3.25 (2H, d, J = 7.6 Hz, H-1 ), 5.17 (1H, t, J = 7.6 Hz, H-2 ), 1.72 (3H, s, H-4 ), 1.62 (3H, s, H-5 ), (1H, s, H), 9.28 (1H, s, H), 8.23 (1H, s, H), 1.84 (1H, br s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), 121. (C-3), 181. (C-4), (C-5), 111. (C-6), 162. (C-7), 92.8 (C-8), (C-9), 14.4 (C-1), 19.6 (C-1 ), (C-2 ), (C-3 ), (C-4 ), 16.6 (C-5 ), (C-6 ), 21. (C-1"), (C-2"), 13.7 (C-3"), 17.8 (C-4"), 25.5 (C-5"), 22.4 (C-1 ), (C-2 ), (C-3 ), 17.7 (C-4 ), 25.5 (C-5 ). Licoflavonol (2): 1 H NMR (4 MHz, DMS-d 6 ) δ: 6.49 (1H, s, H-8), 8.3 (1H, d, J = 8.8 Hz, H-2 ), 8.3 (1H, d, J = 8.8 Hz, H-6 ), 6.92 (1H, d, J = 8.8 Hz, H-3 ), 6.92 (1H, d, J = 8.8 Hz, H-5 ), 3.24 (2H, d, J = 7.2 Hz, H-1 ), 5.19 (1H, t, J = 7.2 Hz, H-2 ), 1.76 (3H, s, H-4 ), 1.65 (3H, s, H-5 ), (1H, s, H), 1.81 (1H, s, H), 1.9 (1H, s, H), 9.35 (1H, s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), 135. (C-3), (C-4), (C-5), 11.2 (C-6), (C-7), 92.8 (C-8), 154. (C-9), 12.8 (C-1), (C-1 ), (C-2 ), (C-3 ), (C-4 ),
11 (C-5 ), (C-6 ), 21. (C-1"), (C-2"), 13.6 (C-3"), 17.7 (C-4"), 25.5 (C-5"). Topazolin (21): 1 H NMR (4 MHz, DMS-d 6 ) δ: 6.47 (1H, s, H-8), 7.92 (2H, d, J = 9. Hz, H-2 and H-6 ), 6.94 (2H, d, J = 9. Hz, H-3 and H-5 ), 3.22 (2H, d, J = 7.2 Hz, H-1 ), 5.17 (1H, t, J = 7.2 Hz, H-2 ), 1.73 (3H, s, H-4 ), 1.62 (3H, s, H-5 ), 3.77 (3H, s, 3-CH 3 ), (1H, s, 5-H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), (C-3), (C-4), (C-5), 11.7 (C-6), (C-7), 93. (C-8), (C-9), 13.8 (C-1), 12.7 (C-1 ), 13.1 (C-2 ), (C-3 ), 158. (C-4 ), (C-5 ), 13.1 (C-6 ), 21. (C-1"), (C-2"), 13.6 (C-3"), 17.7 (C-4"), 25.5 (C-5"). Licoisoflavone A (22): 1 H NMR (4 MHz, DMS-d 6 ) δ: 8.13 (1H, s, 2-H), 6.22 (1H, d, J = 2. Hz, H-6), 6.39 (1H, d, J = 2. Hz, H-8), 6.37 (1H, d, J = 8. Hz, H-5 ), 6.74 (1H, d, J = 8. Hz, H-6 ), 3.25 (2H, d, J = 7.2 Hz, H-1 ), 5.18 (1H, t, J = 7.2 Hz, H-2 ), 1.71 (3H, s, H-4 ), 1.62 (3H, s, H-5 ), (1H, s, H), 9.29 (1H, s, H), 1.86 (1H, s, H), 8.25 (1H, s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: 154. (C-2), (C-3), 181. (C-4), (C-5), 98.9 (C-6), (C-7), 93.6 (C-8), (C-9), 14.6 (C-1), 16.6 (C-1 ), (C-2 ), 19.4 (C-3 ), (C-4 ), (C-5 ), (C-6 ), 22.4 (C-1"), (C-2"), 13.6 (C-3"), 17.8 (C-4"), 25.6 (C-5"). Wighteone (23): 1 H NMR (4 MHz, DMS-d 6 ) δ: 8.3 (1H, s, H-2), 6.45 (1H, s, H-8), 7.37(2H, d, J = 8.8 Hz, H-2 and H-6 ), 6.82 (2H, d, J = 8.8 Hz, H-3 and H-5 ), 3.21 (2H, d, J = 7.2 Hz, H-1"), 5.17 (1H, t, J = 7.2 Hz, ), 1.72 (3H, s, H-4"), 1.62 (3H, s, H-5"), (1H, s, H), 1.87 (1H, s, H), 9.58 (1H, s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), (C-3), 18.2 (C-4), (C-5), 111. (C-6), (C-7), 92.9 (C-8), (C-9), 14.2 (C-1), (C-1 ), 13.1 (C-2 ), 115. (C-3 ), (C-4 ), 115. (C-5 ), 13.1 (C-6 ), 21. (C-1"), (C-2"), 13.7 (C-3"), 17.7 (C-4"), 25.5 (C-5"). Allolicoisoflavone B (24): 1 H NMR (4 MHz, DMS-d 6 ) δ: 8.8 (1H, s, H-2), 6.18 (1H, br s, H-6), 6.33 (1H, br s, H-8), 6.41 (1H, d, J = 8.4 Hz, H-5 ), 6.92 (1H, d, J = 8.4 Hz, H-6 ), 6.6 (1H, d, J = 1 Hz, H-1"), 5.63 (1H, d, J = 1 Hz, H-2"), 1.3 (6H, s, H-4" and H-5"), (1H, s, 5-H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), (C-3), (C-4), (C-5), 99.2 (C-6), (C-7), 93.8 (C-8), (C-9), 13.9 (C-1), 19.7 (C-1 ), (C-2 ), 19. (C-3 ), (C-4 ), 17.3 (C-5 ), (C-6 ), (C-1"), (C-2"), 75.8 (C-3"), 27.5 (C-4"), 27.5 (C-5"). 5,7,4'-trihydroxy-3'(3-methylbut-2-enyl)-3-methoxy flavone (25): 1 H NMR (4 MHz, DMS-d 6 ) δ: 6.19 (1H, d, J = 2 Hz, H-6), 6.42 (1H, d, J = 2 Hz, H-8), 7.82 (1H, d, J 11
12 = 2 Hz, H-2 ), 6.96 (1H, d, J = 8.8 Hz, H-5 ), 7.77 (1H, dd, J = 2., 8.4 Hz, H-6 ), 3.28 (2H, d, J = 7.2 Hz, H-1"), 5.33 (1H, t, J = 7.2 Hz, H-2"), 1.73 (3H, s, H-4"), 1.7 (3H, s,h-5"), 3.76 (3H, s, 3-CH 3 ), 12.7 (1H, s, 5-H), 1.85 (1H, s, H), 1.25 (1H, s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), (C-3), (C-4), (C-5), 98.5 (C-6), (C-7), 93.6(C-8), (C-9), 14.2 (C-1), 12.5 (C-1 ), (C-2 ), (C-3 ), 158. (C-4 ), 115. (C-5 ), (C-6 ), 27.8 (C-1"), 12.5 (C-2"), (C-3"), 17.6 (C-4"), 25.5 (C-5"), 59.6 (3-CH 3 ). Lupiwighteone (26): 1 H NMR (4 MHz, DMS-d 6 ) δ: 8.35 (1H, s, H-2), 6.26 (1H, s, H-6), 7.37 (2H, d, J = 8.8 Hz, H-2, 6 ), 6.81 (2H, d, J = 8.8 Hz, H-3, 5 ), 12.9 (1H, s, 5-H). 13 C NMR (1 MHz, DMS-d 6 )δ: (C-2), (C-3), 18.2 (C-4), (C-5), 98.8 (C-6), (C-7), 16. (C-8), (C-9), 14. (C-1), (C-1 ), 13.1 (C-2 ), 115. (C-3 ), (C-4 ), 115. (C-5 ), 13.1 (C-6 ), 21. (C-1"), (C-2"), 13.8 (C-3"), 17.7 (C-4"), 25.5 (C-5"). Licoarylcoumarin (27): 1 H NMR (4 MHz, DMS-d 6 ) δ: 7.88 (1H, s, H-4), 6.4 (1H, s, H-6), 6.34 (1H, br s, H-3 ), 6.25 (1H, br d, J = 8. Hz, H-5, 2"), 7.6 (1H, d, J =8. Hz, H-6 ), 4.84 (2H, m, H-3"), 1.61 (6H, s, H-4", 5"), 3.81 (3H, s, 5-CH 3 ), 9.37 (2H, br s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: 16.1 (C-2), (C-3), (C-4), (C-5), 96.1 (C-6), (C-7), 12.7 (C-8), (C-9), (C-1), (C-1 ), (C-2 ), 12.7 (C-3 ), (C-4 ), 16.2 (C-5 ), (C-6 ), 4.3 (C-1"), (C-2"), 18.1 (C-3"), 29.3 (C-4"), 29.3 (C-5"). Isolicoflavonol (28): 1 H NMR (4 MHz, DMS-d 6 ) δ: 6.18 (1H, s, H-6), 6.42 (1H, s, H-8), 7.91 (1H, s, H-2 ), 6.94 (1H, d, J = 8.4 Hz, H-5 ), 7.88 (1H, d, J =8.4 Hz, H-6 ), 3.28 (2H, d, J = 7.2 Hz, H-1"), 5.3 (1H, t, J = 7.2 Hz, H-2"), 1.71 (3H, s, H-4"), 1.7 (3H, s, H-5"), (1H, s, 5-H), 1.79 (1H, br s, H), 1.7 (1H, s, H), 9.32 (1H, br s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), (C-3), (C-4), 16.7 (C-5), 98.2 (C-6), (C-7), 93.4 (C-8), 147. (C-9), 13. (C-1), (C-1 ), (C-2 ), (C-3 ), 157. (C-4 ), (C-5 ), 127. (C-6 ), 28.1 (C-1"), (C-2"), (C-3"), 17.7 (C-4"), 25.5 (C-5"). Formononetin (3): 1 H NMR (4 MHz, DMS-d 6 ) δ: 8.31 (1H, s, H-2), 7.95 (1H, d, J = 8.4 Hz, H-5), 6.92 (1H, d, J = 8.4 Hz, H-6), 6.83 (1H, s, H-8), 7.51 (2H, d, J = 8.4 Hz, H-2 and H-6 ), 6.98 (2H, d, J = 8.4 Hz, H-3 and H-5 ), 3.78 (3H, s, 4 -CH 3 ). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), (C-3), (C-4), (C-5), (C-6), (C-7), 12.1 (C-8), 153. (C-9), (C-1), (C-1 ), 13. (C-2 ), (C-3 ), (C-4 ), (C-5 ), 13. (C-6 ), 55.1 (4 -CH 3 ). 12
13 Genkwanin (31): 1 H NMR (4 MHz, DMS-d 6 ) δ:6.85 (1H, s, H-3),6.37 (1H, d, J = 2. Hz, H-6), 6.22 (1H, d, J = 2. Hz, H-8), 7.96 (2H, d, J = 8.4 Hz, H-2 and H-6 ), 6.93 (2H, d, J = 8.4 Hz, H-3 and H-5 ), 3.87 (3H, s, 7-CH 3 ), (1H, s, 5-H), 1.39 (1H, br s, 4 -H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), 14.6 (C-3), (C-4), (C-5), 97.9 (C-6), (C-7),92.7 (C-8), (C-9), 13. (C-1), 121. (C-1 ), (C-2 ), (C-3 ), (C-4 ), (C-5 ), (C-6 ), 56. (7-CH 3 ). Glycycoumarin (33): 1 H NMR (4 MHz, DMS-d 6 ) δ: 7.81 (1H, s, H-4), 6.61 (1H, s, H-8), 6.37 (1H, br s, H-3 ), 6.25 (1H, br d, J = 8.4 Hz, H-5 ), 7.11 (1H, d, J = 8.4 Hz, H-6 ), 3.23 (2H, d, J = 6. Hz, H-1"), 5.15 (1H, t, J = 6. Hz, H-2"), 1.73 (3H, s, H-4"), 1.63 (3H, s, H-5"), 3.76 (3H, s, 5-CH 3 ), 1.6 (1H, s, H), 9.4 (2H, br s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), 12.4 (C-3), (C-4), (C-5), (C-6), 16.1 (C-7), 98. (C-8), 153. (C-9), 16.3 (C-1), (C-1 ), (C-2 ), 12.7 (C-3 ), (C-4 ), 16.1 (C-5 ), (C-6 ), 22.3 (C-1"), (C-2"), 13.7 (C-3"), 17.7 (C-4"), 25.5 (C-5"), 62.8 (5-CH 3 ). Isoglabrone (34): 1 H NMR (4 MHz, DMS-d 6 ) δ: 8.21 (1H, s, H-2), 7.85 (1H, d, J = 8.8 Hz, H-5), 6.92 (1H, d, J = 8.8 Hz, H-6), 6.35 (1H, d, J = 2.4 Hz, H-3 ), 6.26 (1H, dd, J = 2.4, 8.4 Hz, H-5 ), 6.98 (1H, d, J = 8.4 Hz, H-6 ), 6.8 (1H, d, J = 1. Hz, H-1"), 5.94 (1H, d, J = 1. Hz, H-2"), 1.46 (6H, s, H-4", 5"), 9.34 (1H, s, H), 9.23 (1H, s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), (C-3), 175. (C-4), (C-5), 18.9 (C-6), (C-7), (C-8), (C-9), 16.2 (C-1), (C-1 ), (C-2 ), 12.7 (C-3 ), (C-4 ), 13.3 (C-5 ), (C-6 ), (C-1"), (C-2"), 77.7 (C-3"), 27.6 (C-4"), 27.6 (C-5"). Glyurallin A (35): 1 H NMR (4 MHz, DMS-d 6 ) δ: 5.39 (1H, s, H-2), 6.27 (1H, s, H-8), 6.95 (1H, d, J = 2. Hz H-3 ), 6.75 (1H, dd, J = 2., 8.4 Hz, H-5 ), 7.3 (1H, d, J = 8.4 Hz, H-6 ), 3.18 (2H, d, J = 6.8 Hz, H-1"), 5.16 (1H, t, J = 6.8 Hz, H-2"), 1.73 (3H, s, H-4"), 1.63 (3H, s, H-5"), 3.74 (3H, s, 5-CH 3 ), 9.78 (1H, s, H), 9.57 (1H, s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: 64.1 (C-2), 16.2 (C-3), (C-4), (C-5), (C-6), (C-7), 99.8 (C-8), (C-9), 12.5 (C-1), (C-1 ), (C-2 ), 98. (C-3 ), (C-4 ), (C-5 ), (C-6 ), 21.9 (C-1"), (C-2"), (C-3"), 17.7 (C-4"), 25.4 (C-5"), 61.5 (5-CH 3 ). 7-methoxy-2',4'-dihydroxy isoflavone (36): 1 H NMR (4 MHz, DMS-d 6 ) δ: 8.21 (1H, s, H-2), 7.99 (1H, d, J = 8.8 Hz, H-5), 7.7 (1H, br d, J = 8.8 Hz, H-6), 7.15 (1H, br s, H-8), 6.36 (1H, br s, H-3 ), 6.26 (1H, br d, J = 7.6 Hz, H-5 ), 6.98 (1H, d, J = 7.6 Hz, H-6 ), 3.91 (3H, s, 7-CH 3 ), 9.35 (br s, H). 13 C NMR (1 MHz, DMS-d 6 )δ: 13
14 154.6 (C-2), 122. (C-3), (C-4), (C-5), (C-6), (C-7), 12.8 (C-8), (C-9), (C-1), 19.9 (C-1 ), (C-2 ), 1.5 (C-3 ), (C-4 ), 16.2 (C-5 ), (C-6 ), 56.1 (7-CH 3 ). 11b-hydroxy-11b,1-dihydromedicarpin (37): 1 H NMR (4 MHz, DMS-d 6 ) δ: 4.2 (1H, d, J = 1.8 Hz, H-2β), 4.66 (1H, dd, J = 3.6, 1.8 Hz, H-2α), 3.89 (1H, dd, J = 3.6, 1. Hz, H-3), 4.9 (1H, d, J = 1. Hz, H-4), 2.19 (1H, m, H-5α), 2.69 (1H, m, H-5β), 1.93 (1H, m, H-6β), 2.73 (1H, m,h-6α), 5.24(1H, s, H-8), 6.37 (1H, d, J = 2.4 Hz, H-3 ), 6.47 (1H, dd, J = 2.4, 8. Hz, H-5 ), 7.22 (1H, d, J = 8. Hz, H-6 ), 3.69 (3H, s, 4 -CH 3 ). 13 C NMR (1 MHz, DMS-d 6 ) δ: 67.5 (C-2), 39.1 (C-3), 82.6 (C-4), 31.4 (C-5), 32. (C-6), (C-7), 17.5 (C-8), (C-9), 66.2 (C-1), 12. (C-1 ), 16. (C-2 ), 95.3 (C-3 ), 16.5 (C-4 ), 17. (C-5 ), (C-6 ), 55.3 (4 -CH 3 ). Kaempferol 3--methyl ether (38): 1 H NMR (4 MHz, DMS-d 6 ) δ: 6.18 (1H, d, J = 1.6 Hz, H-6), 6.42 (1H, d, J = 1.6 Hz, H-8), 7.93 (1H, d, J = 8.8 Hz, H-2, 6 ), 6.94 (1H, d, J = 8.8 Hz, H-3, 5 ), 3.77 (3H, s, 3-CH 3 ), (1H, s, 5-H), 1.59 (br s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), (C-3), (C-4), (C-5), 98.6 (C-6), (C-7), 93.7 (C-8), 16.2 (C-9), 14.1 (C-1), 12.6 (C-1 ), 13.1 (C-2 ), (C-3 ), (C-4 ), (C-5 ), 13.1 (C-6 ), 59.7 (3-CH 3 ). 2-one-4-methoxy-pyran (39): 1 H NMR (4 MHz, DMS-d 6 ) δ: 6.15 (1H, d, J = 1.6 Hz, H-3), 6.25 (1H, dd, J = 1.6, 8.8 Hz, H-5), 7.54 (1H, d, J = 8.8 Hz, H-6), 3.8 (3H, s, 4-CH 3 ). 13 C NMR (1 MHz, DMS-d 6 ) δ: 163. (C-2), 12.6 (C-3), (C-4), 19.6 (C-5), (C-6), 51.7 (4-CH 3 ). Hirtellanine I (4): 1 H NMR (4 MHz, DMS-d 6 ) δ: 8.6 (1H, s, H-2), 7.9 (1H, d, J = 8.4 Hz, H-5), 6.93 (1H, br d, J = 8.4 Hz, H-6), 6.87 (1H, br s, H-8), 6.13 (1H, s, H-5 ), 6.42 (1H, d, J = 9.2 Hz, H-1 ), 5.57 (1H, d, J = 9.2 Hz, H-2 ), 1.37 (6H, s, H-4, 5 ), 3.46 (3H, s, 2 -CH 3 ), 1.81 (1H, s, H), 9.51 (1H, s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), (C-3), (C-4), 127,1 (C-5), 115. (C-6), (C-7), 12.2 (C-8), (C-9), (C-1), 16. (C-1 ), (C-2 ), 16.9 (C-3 ), 154. (C-4 ), 99.2 (C-5 ), (C-6 ), (C-1"), (C-2"), 75.9 (C-3"), 27.6 (C-4"), 27.6 (C-5"), 61.6 (2 -CH 3 ). Glycyrrhiza-isoflavone C (41): 1 H NMR (4 MHz, DMS-d 6 ) δ: 8.2 (1H, s, H-2), 7.9 (1H, d, J = 8.8 Hz, H-5), 6.92 (1H, dd, J = 2.4, 8.8 Hz, H-6), 6.87 (1H, d, J = 2.4 Hz, H-8), 6.6 (1H, s, H-5 ), 2.58 (1H, t, J = 6.4 Hz, H-1 ), 1.71 (1H, t, J = 6.4 Hz, H-2 ), 1.27 (6H, s, H-4, 5 ), 3.43 (3H, s, 2 -CH 3 ), 1.79 (1H, s, H), 9.6 (1H, s, 14
15 H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), (C-3), (C-4), 127,1 (C-5), (C-6), (C-7), 12.2 (C-8), (C-9), (C-1), 15.5 (C-1 ), (C-2 ), 15.5 (C-3 ), (C-4 ), 99.1 (C-5 ), (C-6 ), 16.7 (C-1"), 31.9 (C-2"), 73.9 (C-3"), 26.5 (C-4"), 26.5 (C-5"), 59.8 (2 -CH 3 ). Isoliquiritigenin (42): 1 H NMR (4 MHz, DMS-d 6 )δ: 7.76 (1H, d, J = 16. Hz, H-β), 7.72 (1H, d, J = 16. Hz, H-α), 8.16 (1H, d, J = 8.8 Hz, H-6 ), 6.4 (1H, dd, J = 2.4, 8.8 Hz, H-5 ), 6.28 (1H, d, J = 2.4 Hz, H-3 ), 7.75 (2H, d, J = 8.4 Hz, H-2, 6), 6.84 (2H, d, J = 8.4 Hz, H-3, 5), (1H, s, 2 -H), 1.64 (1H, br s, H), 1.1 (1H, br s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-β), (C-α), (C=), (C-6 ), 18.1 (C-5 ), (C-4 ), 12.6 (C-3 ), 165. (C-2 ), 113. (C-1 ), (C-1), (C-2), (C-3), 16.3 (C-4), (C-5), (C-6). Isoglycycoumarin (43): 1 H NMR (4 MHz, DMS-d 6 ) δ: 7.83 (1H, s, H-4), 6.56 (1H, s, H-8), 6.36 (1H, d, J = 2.4 Hz, H-3 ), 6.27 (1H, dd, J = 2.4, 8.4 Hz, H-5 ), 7.1 (1H, d, J = 8.4 Hz, H-6 ), 2.75 (2H, t, J = 6.8 Hz, H-1"), 1.81 (2H, d, J = 6.8 Hz, H-2"), 1.33 (6H, s, H-4, 5 ), 3.83 (3H, s, 5-CH 3 ), 9.42 (1H, s, H), 9.41 (1H, s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), (C-3), (C-4), 156. (C-5), 16.7 (C-6), (C-7), 99.3 (C-8), (C-9), (C-1), (C-1 ), (C-2 ), 12.7 (C-3 ), (C-4 ), 16.2 (C-5 ), (C-6 ), 16.5 (C-1"), 31.1 (C-2"), 75.7 (C-3"), 26.4 (C-4"), 26.4 (C-5"), 61.9 (5-CH 3 ). Genistein (44): 1 H NMR (4 MHz, DMS-d 6 ) δ: 8.31 (1H, s, H-4), 6.22 (1H, d, J = 2. Hz, H-6), 6.38 (1H, d, J = 2. Hz, H-8), 7.37 (2H, d, J = 8.8 Hz, H-2, 6 ), 6.82 (2H, d, J = 8.8 Hz, H-3, 5 ), (1H, s, 5-H), 1.89 (1H, br s, H), 9.59 (1H, s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: 154. (C-2), (C-3), 18.2 (C-4), 162. (C-5), 99. (C-6), (C-7), 93.7 (C-8), (C-9), 14.5 (C-1), (C-1 ), 13.2 (C-2 ), (C-3 ), (C-4 ), (C-5 ), 13.2 (C-6 ). Kumatakenin B (45): 1 H NMR (4 MHz, DMS-d 6 ) δ: 6.71 (1H, s, H-3), 7.85 (1H, d, J = 8.4 Hz, H-5), 6.89 (1H, dd, J = 2., 8.4 Hz, H-6), 6.96 (1H, d, J = 2. Hz, H-8), 7.9 (2H, d, J = 8.8 Hz, H-2, 6 ), 6.92 (2H, d, J = 8.8 Hz, H-3, 5 ), 1.56 (br s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), 14.4 (C-3), (C-4), (C-5), (C-6), (C-7), 12.4 (C-8), 16.7 (C-9), 116. (C-1), (C-1 ), (C-2 ), (C-3 ), (C-4 ), (C-5 ), (C-6 ). Luteone (46): 1 H NMR (4 MHz, DMS-d 6 ) δ: 8.12 (1H, s, H-2), 6.45 (1H, s, H-8), 6.36 (1H, d, J = 2.4 Hz, H-3 ), 6.26 (1H, dd, J = 2.4, 8.4 Hz, H-5 ), 6.95 (1H, d, J = 8.4 Hz, H-6 ), 3.22 (2H, d, J = 6.8 Hz, H-1"), 5.17 (1H, t, J = 6.8 Hz, H-2"), 1.72 (3H, 15
16 s, H-4"), 1.62 (3H, s, H-5"). 13 C NMR (1 MHz, DMS-d 6 ) δ: 155. (C-2), (C-3), 18.5 (C-4), (C-5), 11.9 (C-6), (C-7), 92.8 (C-8), (C-9), 12.6 (C-1), 18.8 (C-1 ), (C-2 ), 14.3 (C-3 ), (C-4 ), 16.2 (C-5 ), 13.7 (C-6 ), 21. (C-1"), 12.3 (C-2"), (C-3"), 17.7 (C-4"), 25.5 (C-5"). Licocoumarone (47): 1 H NMR (4 MHz, DMS-d 6 ) δ: 7.15 (1H, s, H-3), 6.7 (1H, s, H-7), 6.46 (1H, d, J = 2. Hz, H-3 ), 6.35 (1H, dd, J = 2., 8.4 Hz, H-5 ), 7.56 (1H, d, J = 8.4 Hz, H-6 ), 3.27 (1H, d, J = 6.8 Hz, H-1"), 5.17 (1H, t, J = 6.8 Hz, H-2"), 1.73 (3H, s, H-4"), 1.62 (3H, s, H-5"), 3.94 (3H, s, 4-CH 3 ), 1.14 (1H, s, H), 9.57 (1H, br s, 4 -H), 9.45 (1H, s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: 15.1 (C-2), 1.4 (C-3), (C-4), 19. (C-5), (C-6), 92.2 (C-7), 15.4 (C-8), 17.1 (C-9), (C-1 ), (C-2 ), 13. (C-3 ), (C-4 ), (C-5 ), (C-6 ), 22.4 (C-1"), 124. (C-2"), (C-3"), 17.7 (C-4"), 25.5 (C-5"), 59.8 (4-CH 3 ). Uralenol (49): 1 H NMR (4 MHz, DMS-d 6 ) δ: 6.18 (1H, d, J = 1.6 Hz, H-6), 6.38 (1H, d, J = 1.6 Hz, H-8), 7.44 (1H, d, J = 2. Hz, H-2 ), 7.59 (1H, d, J = 2. Hz, H-6 ), 3.28 (1H, d, J = 6.8 Hz, H-1"), 5.29 (1H, t, J = 6.8 Hz, H-2"), 1.7 (6H, s, H-4", 5"), (1H, s, 5-H), 1.76 (1H, br s, H), 9.66 (1H, s, H), 9.29 (1H, br s, H), 9.91 (1H, s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), (C-3), (C-4), 16.7 (C-5), 98.1 (C-6), (C-7), 93.2 (C-8), (C-9), 13. (C-1), 12.2 (C-1 ), (C-2 ), (C-3 ), (C-4 ), (C-5 ), 128. (C-6 ), 28.2 (C-1"), (C-2"), (C-3"), 17.7 (C-4"), 25.5 (C-5"). Glicoricone (51): 1 H NMR (4 MHz, DMS-d 6 ) δ: 7.99 (1H, s, H-2), 7.9 (1H, d, J = 8.8 Hz, H-5), 6.91 (1H, dd, J = 2.4, 8.8 Hz, H-6), 6.86 (1H, d, J = 2.4 Hz, H-8), 6.23 (1H, s, H-5 ), 3.12 (2H, d, J = 6.8 Hz, H-1"), 5.16 (1H, t, J = 6.8 Hz, H-2"), 1.68 (3H, s, H-4"), 1.62 (3H, s, H-5"), 3.35 (3H, s, 2 -CH 3 ), 1.72 (1H, s, H), 9.3 (1H, s, H), 8.92 (1H, s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), (C-3), (C-4), (C-5), (C-6), (C-7), 12.1 (C-8), (C-9), (C-1), 14.4 (C-1 ), (C-2 ), (C-3 ), (C-4 ), 98.5 (C-5 ), (C-6 ), 22.4 (C-1"), (C-2"), (C-3"), 17.6 (C-4"), 25.5 (C-5"), 6.4 (3H, s, 2 -CH 3 ). Pratensein (52): 1 H NMR (4 MHz, DMS-d 6 ) δ: 8.33 (1H, s, H-2), 6.23 (1H, d, J = 1.6 Hz, H-6), 6.39 (1H, d, J = 1.6 Hz, H-8), 7.3 (1H, d, J = 1.2 Hz, H-2 ), 6.97 (1H, d, J = 8.4 Hz, H-5 ), 4.94 (1H, dd, J = 1.2, 8.4 Hz, H-6 ), 3.79 (3H, s, 4 -CH 3 ), 1.88 (1H, s, H), (1H, s, 5-H), 9.5 (1H, s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), (C-3), 18.1 (C-4), 162. (C-5), 99. (C-6), (C-7), 93.7 (C-8), (C-9), 14.5 (C-1), (C-1 ), (C-2 ), (C-3 ), (C-4 ), 16
17 112. (C-5 ), (C-6 ), 55.7 (3H, s, 4 -CH 3 ). Dehydroglyasperin C (53): 1 H NMR (4 MHz, DMS-d 6 ) δ: 4.83 (2H, s, H-2), 6.64 (1H, s, H-4), 6.14 (1H, s, H-8), 6.33 (1H, d, J = 2. Hz, H-3 ), 6.24 (1H, dd, J = 2., 8.4 Hz, H-5 ), 7.3 (1H, d, J = 8.4 Hz, H-6 ), 3.14 (2H, d, J = 6. Hz, H-1"), 5.13 (1H, t, J = 6. Hz, H-2"), 1.7 (3H, s, H-4"), 1.62 (3H, s, H-5"), 3.64 (3H, s, 5-CH 3 ), 9.56 (1H, s, H), 9.5 (1H, s, H), 9.36 (1H, s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: 67.2 (C-2), (C-3), (C-4), 158. (C-5), (C-6), (C-7), 98.4 (C-8), (C-9), (C-1), 12.8 (C-1 ), (C-2 ), 16.8 (C-3 ), (C-4 ), 18.7 (C-5 ), (C-6 ), 22.1 (C-1"), (C-2"), (C-3"), 17.6 (C-4"), 25.5 (C-5"), 61.6 (3H, s, 5-CH 3 ). Homobutein (54): 1 H NMR (4 MHz, DMS-d 6 ) δ: 7.79 (1H, d, J = 15.6 Hz, H-β), 7.73 (1H, d, J = 15.6 Hz, H-α), 8.2 (1H, d, J = 9.2 Hz, H-6 ), 6.42 (1H, dd, J = 2., 9.2 Hz, H-5 ), 6.28 (1H, d, J = 2. Hz, H-3 ), 7.53 (1H, d, J = 2. Hz, H- ), 7.28 (1H, dd, J = 2., 8. Hz, H- ), 6.84 (1H, d, J = 8. Hz, H- ), 3.87 (3H, s, 3-CH 3 ), 1.72 (1H, br s, H), (1H, s, 2 -H), 9.75 (1H, s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-β), (C-α), (C=), (C-6 ), 18. (C-5 ), (C-4 ), 12.5 (C-3 ), (C-2 ), 113. (C-1 ), (C-1), (C-2), (C-3), 148. (C-4), (C-5), (C-6), 55.8 (4-CH 3 ). 6-C-prenylorobol (55): 1 H NMR (4 MHz, DMS-d 6 ) δ: 8.26 (1H, s, H-2), 6.45 (1H, s, H-8), 6.99 (1H, d, J = 1.6 Hz, H-2 ), 6.79 (1H, dd, J = 1.6, 8.4 Hz, H-6 ), 6.77 (1H, d, J = 8.4 Hz, H-5 ), 3.23 (2H, d, J = 7.2 Hz, H-1"), 5.17 (1H, t, J = 7.2 Hz, H-2"), 1.72 (3H, s, H-4"), 1.62 (3H, s, H-5"), (1H, s, 5-H), 1.89 (1H, br s, H), 9.5 (1H, br s, H), 8.99 (1H, br s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), (C-3), 18.2 (C-4), (C-5), (C-6), (C-7), 92.8 (C-8), (C-9), 14.2 (C-1), (C-1 ), (C-2 ), (C-3 ), (C-4 ), 111. (C-5 ), (C-6 ), 21. (C-1"), (C-2"), 13.6 (C-3"), 17.7 (C-4"), 25.4 (C-5"). Kaempferol (56): 1 H NMR (4 MHz, DMS-d 6 ) δ: 6.44 (1H, d, J = 2. Hz, H-6), 6.19 (1H, d, J = 2. Hz, H-8), 8.4 (2H, d, J = 8.8 Hz, H-2, 6 ), 6.93 (2H, d, J = 8.8 Hz, H-3, 5 ), (1H, s, 5-H), 1.82 (1H, br s, H), 1.13 (1H, br s, H), 9.38 (1H, br s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), (C-3), (C-4), 16.7 (C-5), 98.2 (C-6), (C-7), 93.5 (C-8), (C-9), 13. (C-1), (C-1 ), (C-2 ), (C-3 ), (C-4 ), (C-5 ), (C-6 ). Gancaonin L (57): 1 H NMR (4 MHz, DMS-d 6 ) δ: 8.35 (1H, s, H-2), 6.31 (1H, s, H-8), 7. (1H, d, J = 1.6 Hz, H-2 ), 6.77 (1H, dd, J = 1.6, 8.4 Hz, H-6 ), 6.81 (1H, d, 17
18 J = 8.4 Hz, H-5 ), 3.31 (2H, d, J = 7.2 Hz, H-1"), 5.15 (1H, t, J = 7.2 Hz, H-2"), 1.75 (3H, s, H-4"), 1.63 (3H, s, H-5"), (1H, s, 5-H), 1.81 (1H, s, H), 9.5 (1H, s, H), 8.98 (1H, s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: 154. (C-2), (C-3), 18.5 (C-4), (C-5), 98.4 (C-6), (C-7), 15.8 (C-8), (C-9), 14.4 (C-1), (C-1 ), (C-2 ), (C-3 ), (C-4 ), (C-5 ), (C-6 ), 21. (C-1"), (C-2"), 131. (C-3"), 17.7 (C-4"), 25.4 (C-5"). Licoisoflavanone (58): 1 H NMR (4 MHz, DMS-d 6 ) δ: 4.29 (1H, dd, J = 5.6, 1.8 Hz, H-2β), 4.41 (1H, dd, J = 5.6, 1.8 Hz, H-2α), 4.52 (1H, t, J = 1.8 Hz, H-3), 5.89 (2H, s, H-6, 8), 6.27 (1H, d, J = 8.4 Hz, H-5 ), 6.83 (1H, d, J = 8.4 Hz, H-6 ), 6.69 (1H, d, J = 1. Hz, H-1 ), 5.67 (1H, d, J = 1. Hz, H-2 ), 1.34 (2H, s, H-4, 5 ), (1H, br s, 5-H). 13 C NMR (1 MHz, DMS-d 6 ) δ: 69.8 (C-2), 46.3 (C-3), (C-4), (C-5), 96. (C-6), (C-7), 94.9 (C-8), (C-9), 12. (C-1), 117. (C-1 ), 15.8 (C-2 ), 17.9 (C-3 ), (C-4 ), 11.2 (C-5 ), 13.1 (C-6 ), (C-1"), (C-2"), 75.1 (C-3"), 27.4 (C-4"), 27.4 (C-5"). Abiochanin A (59): 1 H NMR (4 MHz, DMS-d 6 ) δ: 8.34 (1H, s, H-2), 6.21 (1H, d, J = 1.6 Hz, H-6), 6.37 (1H, d, J = 1.6 Hz, H-8), 7.5 (2H, d, J = 8.8 Hz, H-2, 6 ), 7. (2H, d, J = 8.8 Hz, H-3, 5 ), 3.79 (3H, s, 4 -CH 3 ), (1H, br s, 5-H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), 123. (C-3), (C-4), (C-5), 99.3 (C-6), (C-7), 93.9 (C-8), (C-9), 14. (C-1), (C-1 ), 13.1 (C-2 ), (C-3 ), (C-4 ), (C-5 ), 13.1 (C-6 ), 55.2 (4 -CH 3 ). Liquiritigenin (6): 1 H NMR (4 MHz, DMS-d 6 ) δ: 5.37 (1H, dd, J = 2.4, 12.8 Hz, H-2), 3.3 (1H, dd, J = 12.8, 16.4 Hz, H-3α), 2.55 (1H, dd, J = 2.4, 16.4 Hz, H-3β), 7.56 (1H, d, J = 8.4 Hz, H-5), 6.37 (1H, dd, J = 1.2, 8.4 Hz, H-6), 6.16 (1H, d, J = 1.2 Hz, H-8), 7.3 (2H, d, J = 8.8 Hz, H-2, 6 ), 6.78 (2H, d, J = 8.8 Hz, H-3, 5 ). 13 C NMR (1 MHz, DMS-d 6 ) δ: 78.7 (C-2), 43.3 (C-3), (C-4), (C-5), (C-6), (C-7), 12.7 (C-8), (C-9), 112. (C-1), (C-1 ), (C-2 ), (C-3 ), (C-4 ), (C-5 ), (C-6 ). Licoflavone A (61): 1 H NMR (4 MHz, DMS-d 6 )δ: 6.7 (1H, s, H-3), 7.66 (1H, s, H-5), 6.98 (1H, s, H-8), 7.89 (2H, d, J = 8.8 Hz, H-2, 6 ), 6.92 (2H, d, J = 8.8 Hz, H-3, 5 ), 3.3 (1H, d, J = 7.6 Hz, H-1 ), 5.32 (1H, t, J = 7.6 Hz, H-2 ), 1.73 (3H, s, H-4 ), 1.68 (3H, s, H-5 ), 1.86 (1H, br s, H), 1.24 (1H, s, H). 13 C NMR (1 MHz, DMS-d 6 )δ: (C-2), 14.4 (C-3), (C-4), (C-5), (C-6), 16.6 (C-7), 11.8 (C-8), (C-9), (C-1), (C-1 ), 128. (C-2 ), (C-3 ), 16.1 (C-4 ), (C-5 ), 128. (C-6 ), 27.5 (C-1"), (C-2"), (C-3"), 17.6 (C-4"), 25.6 (C-5"). 18
19 Glyasperin C (62): 1 H NMR (4 MHz, DMS-d 6 ) δ: 4.1 (1H, br d, J = 8.8 Hz, H-2), 3.87 (1H, t, J = 8.8 Hz, H-2), 3.2 (1H, m, H-3), 3.14 (1H, m, H-4), 2.72 (1H, m, H-4), 6.1 (1H, s, H-8), 6.33 (1H, d, J = 2. Hz, H-3 ), 6.19 (1H, dd, J = 2., 8.4 Hz, H-5 ), 6.86 (1H, d, J = 8.4 Hz, H-6 ), 3.42 (1H, d, J = 6. Hz, H-1 ), 5.14 (1H, t, J = 6. Hz, H-2 ), 1.69 (3H, s, H-4 ), 1.61 (3H, s, H-5 ), 3.6 (3H, s, 5-CH 3 ), 9.37 (1H, s, H), 9.18 (1H, s, H), 9.11 (1H, s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: 69.2 (C-2), 3.8 (C-3), 25.5 (C-4), (C-5), (C-6), (C-7), 98.7 (C-8), (C-9), 16.8 (C-1), 118. (C-1 ), (C-2 ), 12.6 (C-3 ), (C-4 ), 16.3 (C-5 ), (C-6 ), 22.3 (C-1"), (C-2"), (C-3"), 17.7 (C-4"), 25.5 (C-5"), 6. (5-CH 3 ). Daidzein (63): 1 H NMR (4 MHz, DMS-d 6 ) δ: 8.26 (1H, s, H-2), 7.94 (1H, d, J = 8.8 Hz, H-5), 6.92 (1H, dd, J = 2., 8.8 Hz, H-6), 6.84 (1H, d, J = 2. Hz, H-8), 7.37 (2H, d, J = 8.8 Hz, H-2, 6 ), 6.8 (2H, d, J = 8.8 Hz, H-3, 5 ). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), (C-3), (C-4), (C-5), (C-6), (C-7), 12.1 (C-8), (C-9), (C-1), (C-1 ), 13. (C-2 ), (C-3 ), (C-4 ), (C-5 ), 13. (C-6 ). 3-methoxy-9-hydroxy-pterocarpan (64): 1 H NMR (4 MHz, DMS-d 6 ) δ: 3.59 (2H, m, H-2), 5.23 (1H, m, H-3), 5.53 (1H, d, J = 5.6 Hz, H-4), 7.27 (1H, d, J = 8. Hz, H-5), 6.5 (1H, br d, J = 8. Hz, H-6), 6.43 (1H, br s, H-8), 7.22 (1H, d, J = 8. Hz, H-6 ), 6.44 (1H, br d, J = 8. Hz, H-5 ), 6.29 (1H, br s, H-3 ), 3.69 (3H, s, 7-CH 3 ), 9.68 (1H, s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: 65.9 (C-2), 38.9 (C-3), 78.1 (C-4), (C-5), 19.7 (C-6), 16. (C-7), 12.9 (C-8), (C-9), (C-1), (C-1 ), (C-2 ), 96.4 (C-3 ), 16.4 (C-4 ), 16. (C-5 ), (C-6 ), 55.3 (7-CH 3 ). 1-methoxyphaseollin (65): 1 H NMR (4 MHz, DMS-d 6 ) δ: 3.52 (1H, t, J = 1. Hz, H-2), 3.44 (1H, m, H-2), 4.16 (1H, dd, J = 4.4, 9.8 Hz, H-3), 5.58 (1H, d, J = 6.8 Hz, H-4), 5.92 (1H, d, J = 1.6 Hz, H-6), 6.1 (1H, d, J = 1.6 Hz, H-8), 6.26 (1H, d, J = 8. Hz, H-5 ), 7.4 (1H, d, J = 8. Hz, H-6 ), 6.34 (1H, d, J = 1. Hz, H-1"), 5.67 (1H, d, J = 1. Hz, H-2"), 1.34 (3H, s, H-4"), 1.33 (3H, s, H-5"), 3.79 (3H, s, 5-CH 3 ), 9.79 (1H, br s, 7-H). 13 C NMR (1 MHz, DMS-d 6 ) δ: 65.8 (C-2), 38.4 (C-3), 75.7 (C-4), (C-5), 92.8 (C-6), 16.7 (C-7), 95.4 (C-8), 157. (C-9), 1.2 (C-1), (C-1 ), (C-2 ), 15. (C-3 ), (C-4 ), 17.7 (C-5 ), (C-6 ), 116. (C-1"), (C-2"), 75.5 (C-3"), 27.3 (C-4"), 27.5 (C-5"), 55.6 (5-CH 3 ). Glabridin (66): 1 H NMR (4 MHz, DMS-d 6 ) δ: 3.91 (1H, t, J = 1. Hz, H-2), 19
20 4.1 (1H, m, H-2), 3.31 (1H, m, H-3), 2.86 (1H, dd, J = 11.2, 15.6 Hz, H-4), 2.68 (1H, br dd, J = 3.6, 15.6 Hz, H-4), 6.86 (1H, d, J = 8.4 Hz, H-5), 6.34 (1H, d, J = 8.4 Hz, H-6), 6.18 (1H, d, J = 2.4 Hz, H-3 ), 6.28 (1H, dd, J = 2.4, 8.4 Hz, H-5 ), 6.82 (1H, d, J = 8.4 Hz, H-6 ), 6.57 (1H, d, J = 1. Hz, H-1"), 5.63 (1H, d, J = 1. Hz, H-2"), 1.36 (3H, s, H-4"), 1.35 (3H, s, H-5"). 13 C NMR (1 MHz, DMS-d 6 ) δ: 69.3 (C-2), 29.9 (C-3), 31. (C-4), (C-5), 18.9 (C-6), (C-7), 17.6 (C-8), 152. (C-9), (C-1), (C-1 ), 15.5 (C-2 ), 12.5 (C-3 ), (C-4 ), 18. (C-5 ), (C-6 ), (C-1"), 13.1 (C-2"), 75.3 (C-3"), 27.3 (C-4"), 27.3 (C-5"). Isolupalbigenin (67): 1 H NMR (4 MHz, DMS-d 6 ) δ: 8.32 (1H, s, H-2), 6.29 (1H, s, H-6), 7.22 (1H, d, J = 2. Hz, H-2 ), 6.82 (1H, d, J = 8.4 Hz, H-5 ), 7.18 (1H, dd, J = 2., 8.4 Hz, H-5 ), 3.31 (2H, d, J = 7.6 Hz, H-1"), 5.3 (1H, t, J = 7.6 Hz, H-2"), 1.75 (3H, s, H-4"), 1.68 (3H, s, H-5"), 3.23 (2H, d, J = 6.8 Hz, H-1 ), 5.15 (1H, t, J = 6.8 Hz, H-2 ), 1.68 (3H, s, H-4 ), 1.63 (3H, s, H-5 ), 12.9 (1H, s, 5-H), 9.55 (1H, br s, H), 8.4 (1H, br s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), (C-3), 182. (C-4), (C-5), 98.8 (C-6), (C-7), 15.8 (C-8), (C-9), 14. (C-1), (C-1 ), (C-2 ), (C-3 ), 155. (C-4 ), 15.9 (C-5 ), (C-6 ), 21. (C-1"), (C-2"), 13.1 (C-3"), 17.7 (C-4"), 25.5 (C-5"), 28.2 (C-1 ), (C-2 ), (C-3 ), 17.7 (C-4 ), 25.5 (C-5 ). 6,8-diprenylgenistein (68): 1 H NMR (4 MHz, DMS-d 6 ) δ: 8.33 (1H, s, H-2), 7.37 (2H, d, J = 8.8 Hz, H-2, 6 ), 6.81 (2H, d, J = 8.4 Hz, H-3, 5 ), 3.4 (2H, d, J = 7.2 Hz, H-1"), 5.14 (1H, t, J = 7.2 Hz, H-2"), 1.76 (3H, s, H-4"), 1.63 (3H, s, H-5"), 3.3 (2H, d, J = 7.2 Hz, H-1 ), 5.12 (1H, t, J = 7.2 Hz, H-2 ), 1.73 (3H, s, H-4 ), 1.62 (3H, s, H-5 ), 13.2 (1H, s, 5-H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), (C-3), 18.1 (C-4), (C-5), (C-6), (C-7), 16.2 (C-8), (C-9), 17. (C-1), (C-1 ), 13.1 (C-2 ), 115. (C-3 ), (C-4 ), 115. (C-5 ), 13.1 (C-6 ), 21.5 (C-1"), (C-2"), 13.1 (C-3"), 17.8 (C-4"), 25.5 (C-5"), 21.5 (C-1 ), (C-2 ), 13.8 (C-3 ), 17.8 (C-4 ), 25.5 (C-5 ). 2'-hydroxyisolupalbigenin (69): 1 H NMR (4 MHz, DMS-d 6 ) δ: 8.2 (1H, s, H-2), 6.31 (1H, s, H-6), 6.36 (1H, d, J = 8.4 Hz, H-5 ), 6.75 (1H, d, J = 8.4 Hz, H-6 ), 3.25 (2H, d, J = 7.2 Hz, H-1"), 5.16 (1H, t, J = 7.2 Hz, H-2"), 1.75 (3H, s, H-4"), 1.62 (3H, s, H-5"), 3.34 (2H, d, J = 7.2 Hz, H-1 ), 5.18 (1H, t, J = 7.2 Hz, H-2 ), 1.71 (3H, s, H-4 ), 1.63 (3H, s, H-5 ), (1H, s, 5-H), 9.27 (1H, s, H), 8.24 (1H, s, H), 1.8 (1H, br s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: 154. (C-2), 12.8 (C-3), (C-4), (C-5), 98.4 (C-6), (C-7), 16.6 (C-8), 155. (C-9), 14.6 (C-1), 19.6 (C-1 ), (C-2 ), (C-3 ), (C-4 ), 15.8 (C-5 ), (C-6 ), 21. (C-1"), (C-2"), (C-3"), 17.7 (C-4"), 25.5 (C-5"), 22.3 (C-1 ), 2
21 123.5 (C-2 ), 131. (C-3 ), 17.7 (C-4 ), 25.5 (C-5 ). Isoderrone (7): 1 H NMR (4 MHz, DMS-d 6 ) δ: 8.38 (1H, s, H-2), 6.23 (1H, d, J = 2. Hz, H-6), 6.4 (1H, d, J = 2. Hz, H-8), 7.28 (1H, d, J = 2.4 Hz, H-2 ), 6.8 (1H, d, J = 8. Hz, H-5 ), 7.29 (1H, dd, J = 2.4, 8. Hz, H-6 ), 6.45 (1H, d, J = 1. Hz, H-1"), 5.79 (1H, d, J = 1. Hz, H-2"), 1.39 (6H, s, H-4", 5"), (1H, s, 5-H), 1.93 (1H, br s, 7-H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), (C-3), 18. (C-4), 162. (C-5), 99. (C-6), (C-7), 93.7 (C-8), (C-9), 14.4 (C-1), (C-1 ), (C-2 ), 12.7 (C-3 ), (C-4 ), (C-5 ), (C-6 ), (C-1"), (C-2"), 76.3 (C-3"), 27.7 (C-4"), 27.7 (C-5"). Licoricidin (71): 1 H NMR (4 MHz, DMS-d 6 ) δ: 3.85 (1H, t, J = 1. Hz, H-2), 4.8 (1H, br d, J = 1. Hz, H-2), 3.31 (1H, m, H-3), 2.77 (1H, dd, J = 4., 16. Hz, H-4), 2.61 (1H, dd, J = 1.8, 16. Hz, H-4), 6.9 (1H, s, H-8), 6.33 (1H, d, J = 8.4 Hz, H-5 ), 6.73 (1H, d, J = 8.4 Hz, H-6 ), 3.14 (1H, m, H-1"), 5.13 (1H, t, J = 6. Hz, H-2"), 1.69 (1H, s, H-4"), 1.62 (1H, s, H-5"), 3.26 (1H, d, J = 6.8 Hz, H-1 ), 5.15 (1H, t, J = 6.8 Hz, H-2 ), 1.71 (3H, s, H-4 ), 1.62 (3H, s, H-5 ), 3.6 (3H, s, 5-CH 3 ), 9.15 (1H, s, H), 9.1 (1H, s, H), 8.16 (1H, s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: 69.3 (C-2), 3.5 (C-3), 26.2 (C-4), (C-5), 16.8 (C-6), (C-7), 98.6 (C-8), (C-9), (C-1), (C-1 ), (C-2 ), (C-3 ), (C-4 ), 17.1 (C-5 ), (C-6 ), 22.3 (C-1"), (C-2"), (C-3"), 17.7 (C-4"), 25.5 (C-5"), 22.5 (C-1 ), (C-2 ), (C-3 ), 17.8 (C-4 ), 25.5 (C-5 ). Glicophenone (72): 1 H NMR (4 MHz, DMS-d 6 ) δ: 4.6 (2H, s, H-α), 6.24 (1H, d, J = 2. Hz, H-3 ), 6.37 (1H, dd, J = 2., 8.8 Hz, H-5 ), 7.96 (1H, d, J = 8.8 Hz, H-6 ), 6.2 (1H, s, H-5), 3.1 (1H, d, J = 6.4 Hz, H-1 ), 5.14 (1H, t, J = 6.4 Hz, H-2 ), 1.68 (3H, s, H-4 ), 1.61 (3H, s, H-5 ), 3.5 (3H, s, 2-CH 3 ). 13 C NMR (1 MHz, DMS-d 6 ) δ: 33.5 (C-α), 23. (C=), (C-2 ), 12.4 (C-3 ), (C-4 ), 18.1 (C-5 ), (C-6 ), (C-1 ), 16.1 (C-1), 158. (C-2), (C-3), 155. (C-4), 98.5 (C-5), (C-6), 22.4 (C-1"), (C-2"), 129. (C-3"), 17.7 (C-4"), 25.5 (C-5"), 6.7 (2-CH 3 ). Licoisoflavone B (73): 1 H NMR (4 MHz, DMS-d 6 ) δ: 8.13 (1H, s, H-2), 6.23 (1H, d, J = 2. Hz, H-6), 6.4 (1H, d, J = 2. Hz, H-8), 6.32 (1H, d, J = 8.4 Hz, H-5 ), 6.89 (1H, d, J = 8.4 Hz, H-6 ), 6.67 (1H, d, J = 1. Hz, H-1 ), 5.68 (1H, d, J = 1. Hz, H-2 ), 1.37 (6H, s, H-4, 5 ), (1H, s, 5-H), 1.89 (1H, br s, H), 8.87 (1H, s, H). 13 C NMR (1 MHz, DMS-d 6 ) δ: (C-2), 12.5 (C-3), 18.6 (C-4), (C-5), 98.9 (C-6), (C-7), 93.7 (C-8), (C-9), 14.6 (C-1), (C-1 ), (C-2 ), 19.7 (C-3 ), (C-4 ), 17.4 (C-5 ), (C-6 ), 117. (C-1"), 21
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